SPE 49467 The Effect of Cloud Point Temperature on Wax Deposition

Sadeghazad, Ayoub, NIOC- Research Institute of Petroleum Industry Christiansen, Richard L., Petroleum Eng. Dep., Colorado School of Mines University

Copyright 1998, Society of Petroleum Engineers, Inc. This paper was selected for presentation at the 8th Abu Dhabi International Petroleum Exhibition and Conference held in Abu Dhabi, U.A.E., 11-14 October 1998 This paper was selected for presentation by an SPE Program Committee following review of information contained in an abstract submitted by the author(s). Contents of the paper, as presented, have not been reviewed by the Society of Petroleum Engineers and are subject to correction by the author(s). The material, as presented, does not necessarily reflect any position of the Society of Petroleum Engineers, its officers, or members. Papers presented at SPE meetings are subject to publication review by Editorial Committees of the Society of Petroleum Engineers. Electronic reproduction, distribution, or storage of any part of this paper for commercial purposes without the written consent of the Society of Petroleum Engineers is prohibited. Permission to reproduce in print is restricted to an abstract of not more than 300 words; illustrations may not be copied. The abstract must contain conspicuous acknowledgment of where and by whom the paper was presented. Write Librarian, SPE, P.O. Box 833836, Richardson, TX 75083-3836, U.S.A., fax 01-972-952-9435.

Introduction Generally, hydrocarbon components may be in the paraffinic, naphthanic, or aromatic forms. Paraffins are non-cyclic hydrocarbons with saturated carbon-carbon bonds. They can have straight or branched chain structure. The paraffins that contribute to wax formation are between C18H38 and C70H142 according to most researchers.[1,2] Wax deposition is an important and serious problem that often occurs in oil production operations. It can occur in producing sands, well-bores, or in the surface transmission lines. Wax deposition is most likely to occur in the well bore and surface transmission lines. However, wax deposits in the reservoir sands may result in serious production losses that are difficult to overcome. Three terms that often arise in discussions of wax formation are paraffin, wax, and rod wax. Paraffin is the combination of paraffinic hydrocarbons. Wax may be defined as the paraffins plus resins, gums, and asphaltic materials. Rod wax consists of wax and oil. A large quantity of oil in the rod wax makes it soft, semifluid, and more readily affected by heat, regardless of the melting point of the wax present, because the oil dissolves and softens part of the wax when the temperature is increased. If very little oil is present, the rod wax is hard and less plastic, and may not be affected by heat until the temperature approaches the melting point of wax in it.[3] Wax deposition is usually characterized by three temperatures: the cloud-point, the pour-point, and the melting-point temperatures. Cloud-point is the temperature at which the first precipitation or crystal of solute is formed.[2] A temperature at which the solution (oil) will not flow when tilted to a horizontal position in the bottle, is called the pour-point.[3] A temperature at which a pure substance liquefies is its meltingpoint. For a pure substance, the cloud-point and the melting point temperatures are equal.

Abstract The main object of this paper is to evaluate and discuss wax deposition problem. It can vary from minor to extremely sever depending on the cloud point temperature, the operating temperature, and the wax content of crude oil. On the other hand, cloud point temperature is related to the solution apparent molecular weight. In other words, cloud point temperature is a function of solute and solvent apparent molecular weights and their mole fractions. Two sets of experiments were performed to analyze the effect of cloud point temperature on wax deposition. The first was solute mole fraction (weight fraction) dependence and the second was solvent dependence experiments. The results indicate that as the apparent molecular weight of solution decreases, the cloud point temperature decreases. So, the lower cloud point temperature, the later precipitation and deposition of wax. As the apparent molecular weight of solute and its mole fraction decreases, the cloud point temperature decreases. Moreover, as the mole fraction of the solvent increases and its apparent molecular weight decreases, the cloud point temperature decreases.

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Controlling Factors in Wax Precipitation The most important wax precipitation controlling factors supported by the literatures and our own experiments, are listed below and briefly explained.

by physical/chemical composition which directly effects the apparent molecular weight. Wax Deposition Mechanisms When wax separates from the solution, it does not necessarily deposit on the pore sands, or pipe walls. There must be other forces or mechanisms[5] to cause it to deposit. The most important mechanisms that cause the deposition of wax are the followings: 1. Alternate coating and draining of the solid surface by the oil.[3] When a solid surface is intermittently coated with oil, the film of oil left on the surface drains away until it is too thin. Its movement is too slow to carry the soft gummy wax particles in suspension.[3] These particles are firmly attached to the surface (or to the previous wax layer) while the oil continues to drain away. 2. High difference between surface and oil temperatures (colder surface). When the surface is much cooler than the oil, a thicker film of oil will remain after each coating because the oil is more viscous.[3] As a result, more wax particles will be deposited. 3. Evaporation of lighter constituents. As the lighter hydrocarbon components vaporize from the coated oil, the concentration of wax goes up in the remaining oil and this causes additional deposition of wax. 4. Diffusion deposition. Previous studies[6] have indicated that diffusion of waxes is the primary wax deposition mechanism. Wax concentration gradient which is due to the temperature gradient, causes the waxes in the solution (oil) to diffuse from the warmer oil which has a greater concentration of dissolved waxes, to the colder oil which has a lower concentration.[7] 5. Gravity deposition. Our experiments indicate that the suspended paraffin particles were going to be settled down with time. This shows that paraffins are deposited with gravity force. Of course, it depends on the specific gravity of solvent. Because the specific gravity of wax is only slightly greater than that of the oil, it remains suspended in the oil and is carried along with it.[3] 6. Shear deposition. The other mechanism contributing to the wax deposition, is shear transport of precipitated waxes to the wall due to the velocity gradient in the flow. The deposition rate increases with increasing shear rate while the flow is laminar, whereas it decreases when the flow becomes turbulent.[6,8] Theory There are many people who have dealt with wax deposition. Most have studied why wax deposition occurs. Some have

1. Temperature. As the temperature of the solution increases,

the solubility of the wax increases.[3] For example, the presence of water, especially bottom water, in the oil string reduces the temperature drop of oil which leads to the reduction of wax deposition. This is due to the fact that specific heat of water is approximately twice that of oil. Therefore, it has twice thermal energy per pound than that of oil. So that, its temperature drop will be the half of the oil temperature drop for the same amount of heat loss.

2. Melting point and molecular weight of wax. At constant

temperature, as the molecular weight of wax/paraffin increases, its melting point also increases, leading to decreasing solubility in solvents.[3] As in tables 1 through 5, this was also supported by our own experiments. From the overall experimental data, it was observed that as the molecular weight of solute or solvent, i.e. the apparent molecular weight of solution (crude) decreases, the cloud point temperature decreases. This leads to the later wax precipitation and deposition.

Reistle[3] reported that melting points of paraffins and waxes vary between 100F and 191F. Where as, we observed that there are some lower molecular weight paraffins ( or paraffinic hydrocarbons), in particular eicosane (C20H42) and octadecane (C18H38) which are important in wax formation, have melting points lower than 100F.

3. Relative proportionality of solvents and solutes. As the

solute fraction in solution decreases, the cloud-point decreases. In other words, as the apparent molecular weight of solution decreases, the cloud point decreases.

4. Pressure. A solution of wax or paraffin in oil deviates in a

positive direction from Raoult's law. So, the solubility of paraffin or wax in solution (crude oil) decreases as the pressure exerted on solution increases.[3] This is due to the fact that the intermolecular forces between like molecules are stronger than between unlike molecules.[4]

5. The nature of the solution. By the nature of solution, we

mean the physical and chemical composition of the solution. The physical composition indicates the amount and the presence of materials that contributed in the solution as water, gas, paraffin, gums, colloidal asphaltic materials, fine sand, silt and etc. As in the figures 1 to 8, our experiments also show that as the physical/chemical composition of the solution is going to be lighter, the cloud point is decreasing. Hence, we will have later precipitation of wax/paraffin. This is reflected

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simulated wax deposition in the formation and pipelines. And, some procedures for preventing or removing wax deposits have been suggested. Most of the published works in this area have referred to the solution temperature and its drop with time as the clue points. However, our experimental results show that besides this, the cloud point temperature, i.e. the precipitation or crystallization temperature of wax/paraffin is the very important and impressive factor in wax/paraffin precipitation. It may be taken as the basic parameter to the problem. On the other hand, the cloud point temperature may be a function of solute and solvent mole fractions and their molecular weights. In most of the literatures, the equation of ideal solution theory for a binary mixture (solid and liquid) has been used to obtain wax/paraffin solubility. [1,4]

directly related to the mole fraction. Our purpose of these experiments was to see how the cloud point temperature varies with respect to the solute, solvent apparent molecular weights. Paraffin, octadecane, and eicosane were used as solutes and the solvents were heptane and decane. The experiments have been done under the standard conditions. I-Solute weight fraction dependence Four different weight fraction of paraffin (solute) were mixed with decane as solvent. They were heated up until there was a single liquid phase (160OF). Then, each of them was slightly cooled down to measure their cloud point temperatures. The results have been given in table 1 and figures 1 and 4. The graphs show that as the mole (weight) fraction of paraffin increases, the cloud point also increases. On the other hand, the comparison of two experiments with different solvents show that as the molecular weight of solvent decreases, the cloud point decreases too. The similar experiments were carried out for the eicosane and octadecane solutes at the same conditions. The results of solutions with eicosane have been tabulated in table 2 and figures 2 and 4, and those of solutions with octadecane have been given in table 3 and figures 3 and 4. II-Solvent dependence This set of experiments can be categorized as single solvent and mixture of solvents. 1-Single solvent. Two different solvents, decane and heptane were used for different mole (weight) fractions of solutes as paraffin, eicosane, and octadecane. a)Decane (solvent). Except solutions with paraffin, eicosane with 0.8 and 0.6 weight fractions, and octadecane with 0.8 weight fraction, the remaining solutions were directly cooled down. On the other hand, each of the above mentioned solution mixtures was heated up to 160OF and then they were slowly cooled down. During the cooling period, the cloud point temperatures were recorded. b)Heptane (solvent). Due to the very low cloud points of octadecane-heptane mixtures and unavailability of laboratory equipment, it was not possible to measure them. Fortunately, the remaining experiments were done successfully. The overall results of single solvent dependence experiments have been shown in tables 1 through 3 and the relevant graphs for each mixture have been shown in figures 5 through 8. 2-Mixture of solvents (decane+heptane). Unfortunately, we could not also do these experiments with octadecane as solute. For the remaining experiments, different compositions of solvents were mixed with different weight fractions of solute.

ln x ps =

H f 1 1 ..(1) R m

This gives the wax solubility, xps (mole fraction), as a function of solution temperature (T), latent heat of solute fusion, and solute melting point temperature in a particular liquid/solid system. For a pure substance the melting point and cloud point temperatures are the same. Where as they will be slightly different for that substance in a solution. On the other hand, wax crystallization or precipitation occurs at the cloud point temperature of the solution. Therefore, it is accurate to use cloud point temperature (Tc), instead of the melting point temperature in the above equation. So, our recommended equation of ideal solution theory for a binary hydrocarbon mixture (precipitated wax/paraffin and crude oil) will take the following form.

ln x ps =

H f 1 1 ..(2) R c

In the solubility equation, solution temperature is the only parameter that changes with time. This leads to the change of the amount of soluble wax/paraffin in the solution. The difference of the last amount of soluble wax and its initial value will give the amount of wax precipitated during that period. Moreover, the solution (crude) temperature through the formation, well bore, or surface transmission lines at any time may be obtained by different correlations and methods.[3,4,9,10,11,12] Experiments The cloud point measuring experiments have been carried out under the two sets of experiments, as solute weight fraction dependence and solvent dependence. The weight fraction is

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Different solvent mixtures were prepared as 20% decane plus 80% heptane, 40% decane plus 60% heptane, 60% decane plus 40% heptane, and 80% decane plus 20% heptane. Then, 0.2, 0.4, 0.6, and 0.8 weight fractions of paraffin were mixed with the corresponding weight fractions of each solvent. The similar solutions were prepared by mixing eicosane and different solvents. The similar procedure of single solvent experiments were also applied to these experiments. The results of this part have been shown in tables 4 and 5 and illustrated in figures 9 and 10. Results and Discussion Figures 1 through 10 represent that all of the cloud point temperature curves have more or less the same slope. This indicates that there must be a relationship between the cloud point temperature, apparent molecular weights of solutes and solvents, and dissolved mole fraction of solute in solvent. This relation may lead to the development of cloud point temperature correlation which will be a function of solvent and solute apparent molecular weights, dissolved mole fraction of solute, and thermal defusion coefficient of solute. However, there are some data a little far from the smooth curve, which was due to the data reading error. The results of solute weight (mole) fraction dependence experiments have been recorded in tables 1 to 3 and illustrated by figures 1 through 4. In addition, the solvent composition dependence experimental results have been recorded in tables 1 to 5 and represented by figures 5 through 10. Conclusions 1. The cloud point temperature of solutions with paraffin was begun by the precipitation of paraffin particles. 2. Unlike paraffin, the cloud points of solutions (crude oil) with eicosane and octadecane were started with the crystallization of eicosane and octadecane. This is because they are pure substances. 3. Temperature and the amount of lighter constituents are the two most important factors affecting wax precipitation and deposition. 4. The apparent molecular weight of solute and its mole fraction are directly related to the cloud point temperature. 5. As the mole fraction solvent increases and its apparent molecular weight decreases, the cloud point temperature decreases. 6. As the apparent molecular weight of solution decreases, the cloud point temperature decreases too. 7. The last three conclusions show that there must be a relation between the cloud point temperature, apparent molecular weights of solutes and solvents, and dissolved mole fraction of solute in solvent.

Nomenclature Hf = change in latent heat of paraffin fusion, cal/g-mol R = ideal gas constant, 1.987cal/g-mol-K T = solution (crude) temperature, K Tc = cloud point temperature of solution(crude), K Tm = melting point temperature of solute, K xPS = maximum amount of wax soluble in liquid phase, mole fraction References
1. Ring, J.N.; Wattenbarger, R.A.; Keating, James F.; and Peddlbhota, S.:" Simulation of Paraffin Deposition in Reservoirs," SPE Production & Facilities (Feb. 1994), 36-42 2. Tuttle, R.N.:" High-Pour-Point and Asphaltic Crude Oil and Condensates," JPT (June 1983), 1192-96 3. Reistle, C.E.:" Paraffin and Congealing Oil Problems," Bull. USBM (1932), No. 348 4. Smith, J.M.; and Van Ness, H.C.: " Introduction to Chemical Engineering Thermodynamics," McGraw-Hill Book Company, Fourth Ed., 1987 5. Sadeghazad, A.; Chrisriansen, R.L.; Sobhi, G.A.:" Wax Precipitation Factors and Deposition Mechanisms," Third National Chemical Eng. Congress, Ahwaz-IRAN, 1998 6. Burger, E.D.; Perkins, T.K.; and Striegler, J.H.:" Studies of Wax Deposition in The Trans Alaska Pipeline," JPT (June 1981), 1075-86 7. Weingarten, J.S.; and Euchner, J.A.:" Methods For Predicting Wax Precipitation and Deposition," SPE (Feb. 1988), 121-6; Trans., AIME, 285 8. Jessen, F.W.:" Effect of Flow Rate on Paraffin Accumulation in Plastic, Steel, and Coated Pipe," Trans., AIME (1958), 213, 80-83 9. Ramey, H.J., Jr.: Well-bore Heat Transmission, JPT (April 1962) 427-35, Trans., AIME, 225. 10. Whitsitt, N.F. and Dysart, G.R.: The Effect of Temperature on Stimulation Design, JPT (April 1970) 493502, Trans., AIME, 249. 11. Sinclair, A.R.: Heat Transfer Effects in Deep Well Fracturing, JPT (Dec. 1971) 1484-92, Trans., AIME, 251. 12. Sutton, G.D. and Roberts, L.D.:" Paraffin Precipitation During Fracture Stimulation," JPT (Sept. 1974), 997-1004

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Table-1: Cloud point temperatures (F) paraffin with single solvents. Solute (paraffin) weight% Solvent 20 40 60 80 Decane 101.00 113.30 120.10 129.05 Heptane 90.50 108.40 116.80 126.40

Table-2: Cloud point temperatures (F) eicosane with single solvents. Solute (eicosane) weight% Solvent 20 40 60 80 Decane 51.50 68.60 85.90 93.85 Heptane 46.80 63.3~64.0 75.70 85.60

Table-3: Cloud point temperatures (F) octadecane with single solvents. Solute (octadecane) weight% Solvent 20 40 60 80 Decane 37.15 52.60 65.05 73.95

Table-4: Cloud point temperatures (F) paraffin mixtures (D=Decane and H=Heptane). Solute (paraffin) weight% Solvent 20 40 60 0.2D+0.8H 95.60 108.60 116.60 0.4D+0.6H 96.50 108.75 118.70 0.6D+0.4H 96.80 109.30 119.10 0.8D+0.2H 97.05 109.95 119.90

with solvent 80 127.90 128.50 128.65 128.80

Table-5: Cloud point temperatures (F) eicosane mixtures (D=Decane and H=Heptane). Solute (eicosane) weight% Solvent 20 40 60 0.2D+0.8H 47.60 64.00 76.10 0.4D+0.6H 49.90 65.60 76.95 0.6D+0.4H 50.20 66.50 77.90 0.8D+0.2H 50.85 67.70 80.30

with solvent 80 86.70 86.80 86.90 87.25

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140 Cloud-point Temperature ( F) 120 100 80 60 40 20 0 0 0.2 0.4 0.6 0.8 1 Solute Wt.%

Cloud-point Temperature ( F)

100 80 60 40 20 0 0 0.2 0.4 0.6 0.8 1 Solute Wt.%

Fig. 1: Cloud point temperature of solution with decane as solvent and paraffin as solute.

Fig. 2: Cloud point temperature of solution with decane as solvent and eicosane as solute.

o
o

90 80 70 60 50 40 30 20 10 0 0 0.2 0.4 0.6 0.8 1 Solute Wt.%

Cloud-point Temperature ( F)

Cloud-point Temperature ( F)

140 120 100 80 60 40 20 0 0 0.2 0.4 0.6 Solute Wt.%

Paraffin Eicosane Octadecane

0.8

Fig. 3: Cloud point temperature of solution with decane as solvent and octadecane as solute.

Fig. 4: Cloud point temperature comparison of solutions with decane as solvent and paraffin, eicosane, andoctadecane as solutes.

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SADEGHAZAD A. and CHRISTIANSEN R. L.

Cloud-point Temperature ( F)

120 100 80 60 40 20 0 0 0.2 0.4 0.6 0.8 1 Solute Wt.%

Decane Heptane

Cloud-point Temperature ( F)

140

100 90 80 70 60 50 40 30 20 10 0 0 0.2 0.4 0.6 Solute Wt.%

Decane Heptane

0.8

Fig. 5: Cloud point temperature of solutions with decane and heptane as solvents and paraffin as solute.

Fig. 6: Cloud point temperature of solutions with decane and heptane as solvents and eicosane as solute.

90 80 70 60 50 40 30 20 10 0 0 0.2 0.4 0.6 0.8 1 Solute Wt.%

Cloud-point Temperature ( F)

Cloud-point Temperature ( F)

140 120 100 80 60 40 20 0 0 0.2 0.4 0.6 Solute Wt.%

D+Paraffin H+Paraffin D+Eicosane H+Eicosane D+Octadecane

0.8

Fig. 7: Cloud point temperature of solution with decane as solvent and octadecane as solute.

Fig. 8: Cloud point temperature comparison of solutions with decane (D) and heptane (H) as solvents and paraffin, eicosane, and octadecane as solutes.

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135 130

Cloud-point Temperature ( F)

125 120 115 110 105 100 95 90 0 0.1 0.2 0.3 0.4 0 .5 0 .6 0.7 0.8 0 .9 1
Decane
0 .8D + 0 .2H
0 .6D + 0 .4H
0 .4D + 0 .6H
0 .2D + 0 .8H
H e p ta n e

S o lu t e W t . %
Fig. 9: Cloud point temperature of solutions with different solvents plus paraffin as solute.

100 95

Cloud-point Temperature ( F)

90 85 80 75 70 65 60 55 50 45 0 0 .1 0 .2 0 .3 0 .4 0 .5 0 .6 0 .7 0 .8 0 .9 1
Dec ane
0 .8 D + 0 .2 H
0 .6 D + 0 .4 H
0 .4 D + 0 .6 H
0 .2 D + 0 .8 H
H e p ta n e

S o lu t e W t . %

Fig. 10: Cloud point temperature of solutions with different solvents plus eicosane as solute.